Search Documents

By R. A. Nadler and

Specimens of Ti-155A (Ti-5Al-1.3Fe-1.3Cr-1.2Mo), Ti-6Al-4V and Ti-4Al-3Mo-1V were hydrogenated, aged to high strength levels, and subjected to notched stress-rupture tests and tensile tests at two strain rates. Both Ti-6Al-4V and Ti-155A were relatively unaffected by hydrogen in amounts exceeding those found in commercially -produced material. Inconsistencies in the data and a relatively low initial level of ductility prevented an accurate determination of the hydrogen tolerance for aged Ti-4Al-3Mo-1V, but there was no evidence that this alloy was any more susceptible to hydrogen embrittlement than Ti-155A and Ti-6A1-4V. THE metallurgical literature has been considerably enriched in the past five years by the publication of the results of many investigations which were concerned with the effects of hydrogen on titanium and its alloys. Although it is not the authors' intention to provide a complete literature survey of this vast field, it is worthwhile to summarize briefly some of the important factors which influence the embrittling phenomenon in a - B alloys. Some of the influencing factors are those of strain rate, temperature, and composition. Hydrogen embrittlement in a - B titanium alloys is now believed to be a strain-induced phenomenon, and whether or not embrittlement occurs at high hydrogen levels depends largely upon whether sufficient time is available for hydride precipitation. This condition is fulfilled by tensile testing at very slow strain rates or by rupture testing smooth or, preferably, notched specimens over relatively long periods. Conveniently, maximum embrittlement occurs at or near room temperature. The presence B - stabilizing elements, in amounts sufficiently small to prevent an all -B or nearly all -P condition, promotes hydrogen embrittlement and this tendency is believed to be related to the amount of a - B interfacial area present. Aluminum, by increasing the solubility of hydrogen in A titanium, greatly reduces the danger of hydrogen embrittlement, while oxygen has been shown to have detrimental effects.' The preceding discussion is based on experimental work performed on annealed a - P alloys. This early work has shown that annealed Ti-6A1-4V and Ti-155A are relatively insensitive to the embrittling effects of hydrogen.' Although no work has been reported on annealed Ti-4A1-3Mo-lV, the alloy would be expected to exhibit somewhat the same insensitiv-ity as Ti-155A. In sharp contrast to the voluminous literature on annealed titanium alloys is the paucity of reported investigations on materials receiving commercial heat-treatment cycles. To date, the most notable contributions in this field have arisen from two separate investigations on Ti-3Mn-1Fe-1Cr-1V-lMo, the so-called 3Mn comple~. These investigations

Jan 1, 1961

By H. W. Schreiber, G. R. Castle

INTRODUCTION The small mining company faces the dilemma of how to finance the development of its properties. Many of these small companies don't have the financial resources to pay for development costs from their own funds and frequently they do not even have the financial strength to permit them to borrow the money needed for development. A project financing can sometimes be arranged in such a way as to solve this dilemma. A typical project financing will not provide the answer to the "little guy's" problem because most project financings require that the sponsors of the project provide completion undertakings and sometimes other undertakings. These undertakings are often a prerequisite to obtaining financing, and if the sponsor is not financially strong enough to provide the comfort that the lenders require, then the sponsor will have difficulty obtaining financing no matter what undertakings are offered. However, with a little imagination and the right set of circumstances, a project financing can sometimes provide the solution to the small mining company's problem. The Strathcona Sound Project is unusually suited as a case study because the sponsor, Mineral Resources International Limited,(MRI) was able to arrange a project financing for the development of the project even though the lenders probably would not have been willing to loan a similar amount of money direct to MRI based on the full faith and credit of MRI's balance sheet. The way that MRI was able to arrange this financing makes for an interesting story. THE CASE In early 1974, MRI owned 100% of a small to medium sized zinc - lead - silver massive sulfide deposit (Property) located 475 miles north of the Arctic Circle less than two miles from deep water on Strathcona Sound which is a shipping zone in the Canadian Arctic. The Property was situated at a desolate location except for an Eskimo settlement (Arctic Bay) which was about 20 miles west of the Property. In other words, the project required that complete infrastructure would need to be installed in this far northern location. Independent reserve and feasibility studies (Study) had been completed on the Property which confirmed a total of 6,825,000 tons of reserves classified and summarized as shown below on Table I: [ ] These reserves were based on 229 diamond drill holes totalling 58,909 feet and were established on a cut-off grade of 7% zinc and a minimum mining height of seven feet. The overall mining recovery rate was estimated at not less than 85% and not more than 90%. The feasibility study indicated that it would cost an estimated $45,044,000 to develop an underground mine, a concentrator, a town-site, a power plant, storage facility, loading dock, a tailings disposal area and an airstrip on the Property with an annual capacity of 525,000 tons of ore per year. The construction period was expected to take two years and projected capital costs were broken down as set forth below on Table II:

Jan 1, 1985

By A. J. Teplitz, T. Bardeen

In the course of an investigation of lost circulation, a new tool has been developed which gives a qualitative measure of the relative velocity between the fluid column in the borehole and the tool. The position of a diaphragm in the side wall of the instrument depends on the flow through the device. This position is established by using the conductive borehole fluid in a potentiometric circuit. The instrument has high sensitivity and can detect changes in velocity as low as. 5 ft/min. Lost circulation mud additives do not interfere with the satisfactory performance of the tool. In a number of circulation losses of the pressure induced type, the instrument has shown that the losses were confined to extremely narrow zones (less than I ft), indicating that such ruptures occur in a more or less horizontal rather than vertical plane as has often been assumed. This pinpointing of the zone of loss is important in remedial procedures since it allows the treatment to be applied directly to the point of loss rather than to the entire open hole. The device can also be employed for indicating points of entry of water in producing wells. INTRODUCTION The need for an improved means of locating the positions of lost returns zones became evident during an investigation of lost circulation difficulties in the Gulf Coast area.1 With instrumentation available at the time, it had been learned that, contrary to common belief, the position of the thief zone responsible for a given loss seldom coincided with the point of bit penetration at the time the loss was encountered. In the majority of cases, the losses were found to be occurring at some distance removed from the bottom of the hole —sometimes as much as a few thousand feet. This information, along with other observations made during the investigation, led to improved techniques' for dealing with lost circulation problems. Highlighted, however, among the results of this work and of similar studies subsequently conducted in drilling operations in other parts of the country, was the indication that a considerable portion of the difficulty and expense involved in treating prolonged circulation losses is due to the unsystematic application of remedial measures to one or more apertures of unknown position. Basis of Tests It is worth considering that if the troublesome formation could somehow be transported to the surface where it could be directly observed, there would likely be little difficulty in readily effecting a seal. Although this is a decided oversimplification of the situation, it does appear that the chief obstacles to similar ease of handling of a lost circulation zone in a well are lack of visibility and of ready accessibility. The latter handicap is overcome to a considerable extent by placement techniques already in use, and other procedures now in the process of development are expected to offer further improvement. But in the matter of visual observation, the technique to be presently described appears to afford a quite satisfactory substitute.

Jan 1, 1957

By J. Offeringa, C. van der Poel

The report describes scaled model experiments on the recovery of oil from porous sands by the injection of miscible liquids [solvents] and the subsequent recovery of the solvents by water flooding. Special attention has been paid to the scaling problem. Scaling rules are deduced and their correctness is checked by carrying out experiments in tubes of various sizes. Data are submitted on the effect of the viscosity ratio oil-solvent on the efficiency of the displacement process, the viscosity ratio varying from 1.5 to 5,000. Breakthrough recoveries obtained when flooding with kerosene as a solvent, are equal to those obtained in water flooding at the same viscosity ratio, indicating that he phenomenon of viscous fingering is decisive. After breakthrough, however, flooding with a miscible liquid becomes much more efficient than a water flood and this is more pronounced as the viscosity ratio oil-solvent is higher. Although high oil recoveries are obtained and most of the solvent in the sand can be recovered by a subsequent waterdrive, a straight flood with miscible liquids does not appear economically attractive because of the large quantities of solvent required. Therefore, a circulation process is introduced, the features of which are described in this paper. Though by means of this circulation process the amount of solvent required can be drastically reduced, the process is not yet economic. SCOPE OF THE INVESTIGATION The recovery efficiency by water flood of oils of viscosities exceeding 50 cp is low. As interest in production of these highly viscous oils is growing at the moment, it was considered worthwhile to gain basic information on the feasibility of first flooding such oils with a low viscous miscible liquid [solvent] and subsequently producing the latter in a conventional way, e.g. by water flooding. The method has the obvious drawbacks that return on the investment is delayed until water flooding has begun and that it requires the investment of a more valuable product to produce a less valuable one. On the other hand, it may be expected that the displacement of one liquid by another is more efficient when the two liquids are miscible than when they are immiscible. As laboratory data on this point are scanty, the present investigation seemed justified. Another argument for carrying out these experiments is that they present a valuable contribution to our concepts of the scaling problem in reservoir engineering studies. Some major difficulties which are encountered in the scaling of the waterflooding process such as the scaling of the capillary forces and the difficulty of obtaining the same permeability characteristics in the model do not present themselves in this case. As the fluids are miscible capillary forces do not play a role and as there is only one fluid phase, Darcy's law is valid in its original form. Consequently it is felt that the scaling rules can be deduced with a greater amount of certainty. An essential feature of the experiments is that they are scaled model ones, which are, however, somewhat

Jan 1, 1955

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By M. C. Flemings, G. E. Nereo

General expressions are given to describe macro-segregation in castings and ingots which results from mass flow of solute-rich liquid to feed solidification and thermal contractions. Analytical solutions are given for solidification with planar isotherms (unidirectional and bidirectional heat flow). These solutions describe inverse segregation and centerline segregation. Numerical examples are given for A1-4.5 pct Cu alloy. In 1540, Vannoccio Biringuccio published one of the first references to macrosegregation, describing the problem of exudation and inverse segregation in the manufacture of bronze gun barrels.' Since then, a great many studies of macrosegregation have been reported. Recent work of particular engineering interest includes that of Marburg 2 and others:" on centerline segregation and other types of segregation in large steel ingots, and work of Adams,5 Scheil, 6 and Kirkaldy and youdelis7 on inverse segregation in nonferrous ingots. In most studies on this subject, the various types of macrosegregation have been treated as separate phenomena. For example, quite different mechanisms have been proposed for formation of centerline segregation, negative cone of segregation, inverse segregation, banding, and so forth. In this, and in several papers to follow, it is proposed that these as well as other types of macrosegregation result from the same basic mechanism and can be quantitatively described by the same basic equation. It has often been suggested that some types of segregation (such as centerline segregation and banding) occur as a result of buildup of solute at the tips of growing dendrites.2-4 ,8-10 As example, banding can be induced in centrifugal castings by mechanical vibration, and Northcott 10 suggests this might be due to the influence of the vibration on the boundary layer at the dendrite tips of the growing dendrites. However, in view of the extremely small boundary layer known to exist at the tips of the dendrites,11,12 any interpretation of macrosegregation based on this boundary layer is clearly incorrect. Note that experiment has shown that significant buildup of solute does not occur at dendrite tips in ingot solidification, but even if such buildup occurred the thickness of the enriched zone would only be the order of D/U where D is liquid diffusion coefficient and U is dendrite tip velocity. For usual casting or ingot solidification this solute-enriched layer is 10"3 cm, far too small to account, for example, for centerline segregation.11'12 It has also been suggested that convection in the bulk liquid (ahead of the advancing dendrites) might cause segregation by sweeping away the solute-rich boundary layer in front of the dendrites.3 However, since there is no significant boundary layer, this explanation must be incorrect. The convection might directly cause segregation by penetrating between the dendrite arms, and presumably in a rimming steel ingot it is sufficiently vigorous to cause some segregation in this way. Centerline segregation, however, cannot be interpreted as resulting from this convection since a sharply segregated zone is usually found near the centerline, with the bulk of the ingot being nearly of nominal composition. If convection in the bulk liquid were the direct cause, a gradual change in ingot composition over the entire cross section would be expected. It is known that sudden changes in convection of the bulk liquid during solidification can result in banding,14 but it is not clear that the banding results directly from the effect of convection on solute distribution. Changes in convection also affect thermal conditions in the liquid-solid region of a solidifying ingot. It will be seen later in this paper, and in a paper to follow, that macrosegregation is strongly influenced by these thermal changes. Recognizing that in some cases of ingot solidification (as in solidification of rimming steels) convection in the bulk liquid may have a direct effect on solute distribution, we neglect it in this paper and in the several to follow. We then derive general expressions describing macrosegregation which results from the mechanism of interdendritic flow of solute-rich liquid

Jan 1, 1968

By J. H. Lightfoot, Stuart E. Buckley

DEEP drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.1 The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen4,5,6 and by others,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems.9-17 It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 lb. per sq. in. Thus, at pressures of 2500 lb. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 600°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduction. The combined effects of pressure and temperature on condensation and vaporization of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpretation of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate systems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21.22 it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has

Jan 1, 1941

By David E. Hyatt

The chemical attributes of cyanides have long been exploited in ore pro- cessing schemes for the recovery of copper, molybdenum, gold, silver, and other metal values. Blast furnacing operations are significant unintentional producers of cyanides which find their way into process waters. Many of the more than 20,000 electroplating facilities in the United States utilize cyanide plating baths and generate cyanide containing wastes. As social, political, and economic pressures for water quality attainment, maintenance, and preservation grow, the requirements for the development of treatment technology to control cyanide levels in wastewater become increasingly apparent. Just as the chemistry of the cyanide ion 1s an integral part of its industrial applicability, so must this chemistry be a fundamental part of any decomposition or removal technology used to control its level in effluent or recycled waters. The complexity of this chemistry is substantial and it cannot be considered in a superficial or cursory manner if control system design is to be both efficient and reliable.

Jan 1, 1975

By D. T. Van Zandt

IN the late 1920's rotary drills began to replace the churn drills in the petroleum industry, but until the middle 1940's the churn drill was the only widely accepted means of drilling large-diameter blastholes for quarry operations. The Calcite plant of the Michigan Limestone Div., U. S. Steel Corp., was one of the first to experiment with rotary drills for quarry blasthole drilling, and the first to employ compressed air on a fully rotary rig to cool the bit and raise the cuttings to the collar of the blasthole. The Calcite plant operates a limestone quarry near Rogers City, Mich., in the northern part of the lower Michigan peninsula. The formation quarried, a portion of the middle Devonian series, is the Dundee limestone, which is uniform, seldom massive, and characterized by definite bedding planes. The dip is southeast, 40 ft to the mile. Quarry faces vary from 20 to 116 ft in height. Vertical blastholes are used entirely, from three to five rows of holes being drilled parallel to the working face, spaced 18 ft apart with 18-ft burden and drilled 6 to 8 ft below shovel grade. Quarry operations coincide with the navigation season on the Great Lakes, as the bulk of the stone is transported by lake carrier. The normal operating season runs from April to December, the remaining time being devoted to stripping operations and plant and equipment maintenance. In the followirig discussion drilling rates mentioned refer to overall drilling time and include all operations such as moving from hole to hole, penetration and extraction of tools, and routine maintenance. Time consumed by such factors as power delays and major machine repair is not included in drilling time unless otherwise stated. Figures cover only operations at this one plant in the formation mentioned. Needless to say, a very different set of figures could be obtained in a different formation. However, the comparison of footage obtained with churn drills and rotary rigs in this particular formation has been used as an indication of what might be the expected performance of rotary rigs in other formations. Prior to 1950 the bulk of the blasthole drilling at the Calcite plant was done by electrically powered churn drills. Both crawler and wheel-mounted rigs were used. These machines, which mounted a 22-ft drill stem of 4½ in. diam and a spudding type of bit 2 to 4 ft long, drilled a hole of 5 ?-in. diam. Average drilling rate of these rigs in the Rogers City formation was 8 % ft per hr. In 1946 one of the first rotary blasthole drills offered to the quarry industry was put into use on an experimental basis. This machine, known as the Sullivan Model 56 blasthole drill, Fig. 1, was on 16-in. crawler pads and electrically powered at 440 v. The drill bit, a Hughes Tri-Cone roller bit of 5?-in. diam, Type OSC, was threaded into the end of the 4-in. square hollow drill rod or stem. These drill rods were 20 ft long with female threads on one end and male on the other to allow for addition of the desired number of rods for drilling holes of various depth. Rods were handled by a single drum hoist geared to the main drive motor and racked by a 30-ft derrick or mast when not in use. The cable from the hoist drum fed through a crown block on the top of the derrick back to the water swivel mounted in the top end of the drill stem in use. This cable remained attached during drilling operations and was used to hoist the tool string from the hole. Down pressure was applied to the tool string by means of a pair of 4-in. diam hydraulic cylinders acting on the drill chuck holding the drill rod. The first chuck consisted of flat jaws which gripped the flat sides of the stem. These jaws were controlled by set screws forcing them into contact with the drill stem. As these set screws had to be loosened and tightened by hand with each stroke of the hydraulic feed cylinders, there was great delay. For this reason the semi-automatic chuck was developed which automatically gripped the stem on the downward stroke but released for retraction of the hydraulic feed cylinders. Rotation was imparted to the tool string by a rotary table acting on the chuck and geared to the main drive motor through a separate gear train and clutch. A positive displacement water pump, mounted on the drill, fed water through a system of pipes and hose into the water swivel mounted on the top of the drill rod and through the rod and bit, washing the drill cuttings to the collar of the hole. Where water was scarce, provision was made to settle out the cuttings coming from the collar of the hole and re-use the water. Where water was abundant the stream coming from the hole was wasted. Drilling rate with this machine was about 20 ft per hr and bit life 1600 ft of hole. While this rate was more than twice that obtained with the churn drills employed, the problem of water supply and drill cuttings disposal rendered the machine impractical from an operating standpoint. Consequently it was used only in that part of the operation for which water was easily supplied, when the character of the formation made it least difficult to wash cuttings away from the collar of the hole. In October 1949 it was suggested that drill cuttings be removed by compressed air, long used for this purpose on pneumatic drills, and collected at the collar by suction. Thereafter, the water pump on the Sullivan 56 was replaced by a 500-cfm air compressor and a trial run made. Air pressure at

Jan 1, 1955

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By Anthony Folger, Howard R. Lowe, J. F. Dougherty, E. G. Trostel, Joffre Meyer

The status of the natural gas industry in Alberta, Canada, is described with particular reference to the current extent of natural gas reserves and possibilities for additional development. Certain major fields are discussed as representative of the types of gas accumulations within various broad geographical divisions of the provinces. The estimation of the future performance of a gas reservoir is discussed as the basis for an estimate of the future availability of natural gas from presently known reserves. The future availability of the provincial reserves and the estimated future demand for gas within the province are described. INTRODUCTION This paper is a condensation of a detailed study of the natural gas reserves and the future availability of pipeline gas in the province of Alberta as prepared for Trans-Canada Pipe Lines Limited and presented in public hearings at Edmonton and Calgary before the Petroleum and Natural Gas Conservation Board of the Province of Alberta. The study began in October, 1950, and resulted in the preparation of five volumes of data at the expenditure of more than 20,000 man-hours. This paper is designed to afford a broad picture with detail limited to a type example of both natural ga-accumulation and future availability of gas supply. The province of Alberta has an area of 255.285 square miles which, for sake of comparison. is 8,359 square miles smaller than the state of Texas. Natural gas was first discovered in 1883 at the now abandoned Alderson well located some 20 miles southeast of the town of Princess. The first gas in commercial quantities was found at Medicine Hat in 1890. During the last 68 years. 187 localities have been discovered which are capable of gas production, and 73 per cent of these have been found since 1945. Sixty fields currently are producing gas, including 22 non-associated gas accumulations. Location of the oil and gas fields and prospects in the province of Alberta is shown in Fig. 1, together with a list of the localities of measurable gas, Fig. 1A. The estimated total provincial gas reserve as of Jan. 1, 1952, for the 104 fields estimated, is 11.7 trillion cu ft proved and probable, and for the 187 known areas capable of production is in excess of 16 trillion cu ft on a total proved, probable, and possible basis. Five fields (Pincher Creek, Leduc-Woodbend, Viking-Kinsella, Cessford and Medicine Hat) are estimated to have recoverable reserves of more than one trillion cu ft each. A sixth field, Turner Valley, was initially in this group, but its reserves have been depleted substantially. Twenty-four fields, of which the above mentioned six fields are a part, have estimated gas reserves (including the possible category) in excess of 100 billion cu ft. These 24 fields account for 79 per cent of the total provincial reserves. Comparative systemic analyses reflect that 56 per cant of Alberta's gas reserves are contained in sediments of Cretaceous age; 30 per cent in sediments of Mississippian age; 10 per cent in sediments of Devonian age; three per cent in sediments of Triassic age; and the remaining one per cent in Jurassic and Permo-Pennsylvanian sediments. It is expected that the relative importance of the Mississippian, Devonian, and Triassic sediments will be increased as exploration progresses. GENERAL GEOLOGY The western Canada basin comprises the sedimentary area between the Canadian Shield and the Rocky Mountain Front Range, the Arctic Ocean, and the International Boundary. The basin has an approximate area of 765,000 square miles and embraces parts of the provinces of Manitoba. Saskatchewan. Alberta, British Columbia and the Northwest Territories. Generalized columnar sections for the Province of Alberta are shown in Fig. 2. Substantially all of Alberta, except its northeast corner, has sedimentary cover. Sediments of all the geologic systems are represented. except those of Silurian age.

Jan 1, 1952

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941

By Leo F. Reinartz

Part II of a four-part series on the history of steelmaking in the US, points out the inadequate safety and living conditions that existed in steel mills at the turn of the Century. Also defined are furnace and process developments. OPERATIONS in steel plants today are highly mechanized. Men work in light, clean, orderly melting shops, making it difficult for old timers to convince young men that primitive, hazardous conditions existed in steel plants at the turn of the century. Working conditions then were very poor as compared to present day standards. In small plants especially, sanitary, locker, and washroom facilities, first-aid practices and stations were un- known Accidents were frequent and severe. Workers had a fatalistic attitude toward getting hurt. He who had an accident was looked upon as a hero. A dirty bandanna often served as a bandage. Infections were frequent. Electric cranes were in their infancy and broke down often Cables had not as yet replaced chains. Pig iron and scrap iron were loaded by hand in the stockyard, and stockyard locomotives were un- known; mules served as the usual motive power. It was not unusual to see recorded a delay of ½ hr in charging a furnace because of a balky mule. Furnace operations A few plants had primitive charging machines, but most furnaces were charged by placing scrap or pig iron on the paddle of a long peel, which rested on a bar across the furnace door opening. Laborers at the handle end of the peel, using the bar as a fulcrum, would heave the material into the furnace by a down and sideward motion of the peel handle. In time they became expert in placing these materials in the furnace, but it was hard, hot work, and a long time was required for charging. Cold charges of 25 tons required more than 12 hr for melting and re- fining the steel. Ports, doors, and frames were not water cooled. The charging and working area in front of the furnace was covered with steel plates. They were hot and often warped by the intense heat of the un- insulated checker chambers directly below. In the summer, working conditions on the charging floor were almost unbearable. Silica refractories were of poor quality. Because of this, and the inadequate training of furnace men in fuel control and furnace operations, roofs, front and back walls, and ends burned out rapidly. Dolomite machines were unknown; consequently, furnace banks and hearths were fettled with dolomite by the use of hand shovels. The round system required six or more men. Each man took a shovelful of dolomite and, in his turn, deposited it on the back wall and bank by a dexterous forward swing and twist of the shovel. The upward swing of the shovel partially protected his face from the searing heat of the furnace coming out through the wide-open door. Considerable skill and stamina were required to do this job properly. Reverse valves, usually of the cast-iron butterfly type, were located below the charging floor. They were operated by long levers on the charging floor level men they became warped, because of heat and abuse, great strength and skill were required to reverse them. Furnace operations were difficult. The quality and quantity of producer gas coming from irregularly stoked, hand-operated gas producers was uncertain and unreliable. Furnace Linings and ports were quickly burned out. Poor bottom and side-wall refractories, indifferent and inexperienced crews, as well as irregular re-

Jan 1, 1961

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941

By G. W. Brock

Experiments in the form of aging of overstrained tension specimens and elevated temperature tension testing, have been carried out on recrystallized arc-cast molybdenum. The aging behavior of molybdenum was found to be strongly dependent on the degree of plastic strain present in the lattice: the reason for this being the low solid solubility for the common interstitial elements in molybdenum. GEORGE W. BROCK, formerly Research Associate, Department of Theoretical and Applied Mechanics, University of Illinois, Urbana, III., is Research Associate, Department of Engineering Sciences, IBM Research Center, Yorktown Heights, N. Y. Manuscript submitted January 19, 1961. IMD THE term strain aging is familiar in connection with the recovery of the yield point in mild steel after tensile overstraining, and there are other instances where it is known to exert an appreciable effect on mechanical properties. For example, steel exhibits a greater tensile strength at mildly elevated temperatures than at room temperature and serrated stress-strain flow curves occur under certain conditions. It has been known for a number of years that the phenomenon of strain aging is directly connected with the presence of carbon and nitrogen in the lattice; and extremely small amounts of either element are sufficient to produce the effect. In this study, the aging behavior of overstrained tensile specimens of recrystallized molybdenum has

Jan 1, 1962

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By R. H. Jacoby, V. J. Berry

When dry gas is injected into a reservoir containing a volatile crude oil, a significant amount of the reservoir liquid phase may become vaporized. The resultant rich gas phase, when subsequently produced, con-tributes to tank oil production. This contribution assumes greater importance, the more volatile the oil in-olved. Oil recovery may be sub-stantially greater than that predicted by conventional frontal-drive methods, which do not consider the vaporization equilibrium between the reservoir oil phase and the injected gas. A calculation method has been (developed to account for vaporiza-. tion of the reservoir liquid phase during gas-injectiorz operations, and for the tank oil production which results from this factor. Recovery performance calculations are presented for a reservoir containing a highly volatile oil. Tank oil recovery is calculated to be about twice that predicted by the use of the conven-rional frontal-drive equations. In contrastto usual pressure maintenance performance results, in which the gas-oil ratio rises at an increasing rate after gas breakthrough, the pre-dicated gas-oil ratio rises rapidly to about 12,000 scf/bhl and then rises much less rapidly. During gas inje-tion, most of the reservoir liquid phase contacted is evaporated by the dry injection gar. The gas-oil ratio during this period is dependent upon reservoir pressure. The higher the operating pressure, the lower the gas-oil ratio. The predicted behavior i., in accordance with laboratory PVT tests made to .simulate the vaporization behavior. In addition to recovery performance predictions, results of the calculation procedure include complete wellstrearn composition data of value in the design of gasoline plant facilities often used in con-rrction with gas-injection operations. INTRODUCTION In the cycling of gas-condensate reservoirs, dry gas is injected to maintain reservoir pressure during wet gas production and to thereby eliminate or reduce ultimate loss of liquids due to retrograde condensation within the reservoir. Gas injected into crude oil reservoirs has a dual function. It displaces oil to the producing wells and at the same time serves to partially or fully maintain reservoir pressure. Oil shrinkage which would occur upon pressure reduction is thereby minimized or eliminated. Accepted calculation methods are available'= for predicting recovery performance of either gas-condensate reservoirs or crude oil reservoirs which are being subjected to gas injection. In gas-condensate reservoirs, any retrograde liquid formed does not flow, and it is necessary to account only for the vaporization equilibrium between this liquid and the injected gas. Conversely, in normal crude oil reservoirs, both the oil and gas phases flow, but it has not been considered necessary to account for any vaporization of the reservoir liquid which might occur upon contact with the dry injection gas. Recently, high shrinkage reservoir fluids known as "volatile oils" have been found in increasing amounts. These oils are characterized by tank oil gravities above 4.5" API, solution gas-oil ratios above 1,000 scf/bbl, and reservoir volume factors above two. Special techniques have been devised for predicting depletion performance of reservoirs containing such oils.74.5.1; One of the characteristics of reservoirs producing volatile oils is that the reservoir gas phase carries a significant amount of oil which is recoverable as stock-tank liquid. This unusual vaporization be-havior implies that an appreciable amount of reservoir liquid would be vaporized upon contact of the oil with dry injection gas. In a gas-injection operation, tank oil recovery would he obtained not only through frontal displacement of the reservoir liquid by the injected gas, but also through production of the rich gas phase. This means that not only are improved methods needed to predict recovery of such oils from reservoirs undergoing gas injection, but it would also be expected that high oil recoveries might be obtained by such operations. When relatively dry gas is injected in to a volatile oil reservoir, phase equilibrium between the injected gas and the reservoir oil will tend to bc established. Initially the most volatile components, such as propane, the butanes and the pentanes, will account for most of the material transferred from the oil phase to the gas phase. As the partially stripped oil phase is contacted with additional dry injection gas, the heavier intermediate components, such as the hexanes, the heptanes and the octanes, will gradually transfer to the gas phase in increasing amounts. This is because the supply of lighter components in the oil phase dwindles due to the stripping action of the injected gas. This stripping action will usually continue to be effective down

By J. W. Freeman, D. N. Frey

Fundamental reasons for the improvement in creep resistance of an austenitic alloy by cold working were investigated mainly by X-ray diffraction. The creep resistance was found to be improved by the internal stresses in the lattice of the alloy induced by the cold work. THIS investigation was concerned with the fundamental reasons for improvement in creep resistance of an austenitic alloy as a result of cold working. Also, the investigation was carried out to elucidate the conditions under which cold working could be expected to improve the creep resistance. To achieve these ends, creep resistance and internal structure were correlated for a variety of cold-worked conditions. Since the aim of the investigation was not to obtain specific and extensive information on any one alloy, creep testing was done with a single stress at 1200°F. Structural studies were carried out primarily with X-ray diffraction characteristics. The alloy used, low carbon N-155, was selected on the basis of being representative of at least some of the alloys used in gas turbines. Low carbon N-155 alloy in the form of %-in. sq bar stock was used in this investigation. The chemical composition, in percent, was: C, 0.13; Mn, 1.43; Si, 0.34; Cr, 20.73; Ni, 18.92; Co, 19.65; Mo, 3.05; W, 1.98; Cb, 0.98; N, 0.14; and Fe, balance. The bar stock was produced from a 13-in. sq billet, finished to 7/s in. round cornered square between 2060" and 1910°F. Prior to use in this particular investigation, the bar stock was solution-treated 1 hr at 2200°F and water quenched. This procedure was used in order to put the stock in a condition where effects of prior processing were minimized. Experimental Procedure The specific approach to the problem was twofold. First, the influence of cold working, under various conditions, on the creep rate under a single stress at 1200°F and on the internal structure was in part determined. Second, the effect of annealing at various times and temperatures on the creep rate and internal structure of the cold-worked samples was in part evaluated. The first step was basic to the investigation—creep resistance and structure were to be correlated. The second step was taken to see if the annealed samples showed some internal changes which could also be correlated with changes in creep resistance. This it was felt would facilitate solution of the basic problem. The creep and structural studies were carried out on samples reduced approximately 5, 15, and 40 pct at room temperature and 15 pct at temperatures up to 2200 °F. Annealing of various of the samples was done at 1200°, 1400°, 1600°, and 1800°F for time periods up to 1000 hr. Studies of the annealed samples were concentrated on materials rolled approximately 5, 15, and 40 pct at room temperature and 15 pct at 1400°F. The creep tests were carried out at 1200°F under 40,000 psi, the latter being approximately the 1000 hr rupture stress of the material

Jan 1, 1952

By F. Weinberg

The distribution of solute during the progressive solidification of dilute Sn-Ag alloys was determined in both solid and liquid as a jbnction of growth rate, rod diameter, temperature gradient, and solute concentration, using radioactive tracer techniques. The results indicated that partial mixing occurs in the liquid during freezing for most of the conditions investigated, approaching complete mixing for larger rod diameters (>2mm) and slow growth rates. Measured solute distributions were fitted to distribution functions based on diffusion controlled solute transport in the liquid state, by treating the normal solute diffusion constant and distribution coefficient as variable solute transport and segregation parameters. Values of these parameters were determined for the growth conditions investigated. Observations were made to determine whether mixing in the liquid was primarily due to volume changes in freezing or to differences in density between solute and solvent. The former effect was investigated using a selected Sn-Bi alloy as a solvent with zero volume change on fusion, and the density effect was studied using vertical solidifications of Sn-In and Sn-Ag alloys, systems having, respectively, very small and large differences in density between solute and solvent. The result indicate that mixing in the liquid cannot be primarily attributed to either volume changes or density differences. THE solute distribution in progressively solidified rods of dilute alloys, in which there is complete mixing in the liquid, is given by the expression1 where C, is the solute concentration in the solid at the point where the fraction g of the material has solidified, C, is the initial solute concentration and k is the equilibrium distribution coefficient. If it is assumed that there is no significant con-vective mixing in the liquid, then the solute distribution in the initial portion of a semi-infinite rod has been calculated to be2 where t is the time from the start of freezing and x1 is the distance in the liquid ahead of the solid-liquid interface at time t. Expressions [1] and [2] describe the limiting cases of solute distribution in the liquid, i.e., complete mixing, or no convective mixing; in practice it might be expected that the solute distribution would be somewhere between these two cases. pfann3 has suggested that Eq. [I] is applicable for partial mixing, as well as complete mixing, if an effective distribution coefficient k1 is used instead satisfactorily describes solute distributions in rods of magnesium, n-g, and b-sb6 alloys that were progressively solidified from the melt without mechanical mixing. The values of kl were observed to depend on the growth rate4-6 and the temperature gradient.6 The purpose of the present investigation was to measure solute distributions in both the solidified rods and the melt as a function of the solidification variables, and to determine to what extent the observed solute distributions could be described by the above theoretical expressions, keeping in mind that expressions [2] and [3] have been derived solely for the case of diffusion controlled solute transport in the liquid and are not theoretically applicable to

Jan 1, 1963